JPS6380849A - Catalytic system for combustion of high pressure methane based fuel and combustion method using the same - Google Patents
Catalytic system for combustion of high pressure methane based fuel and combustion method using the sameInfo
- Publication number
- JPS6380849A JPS6380849A JP61224837A JP22483786A JPS6380849A JP S6380849 A JPS6380849 A JP S6380849A JP 61224837 A JP61224837 A JP 61224837A JP 22483786 A JP22483786 A JP 22483786A JP S6380849 A JPS6380849 A JP S6380849A
- Authority
- JP
- Japan
- Prior art keywords
- combustion
- platinum
- palladium
- catalyst system
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 238000002485 combustion reaction Methods 0.000 title claims abstract description 78
- 239000000446 fuel Substances 0.000 title claims abstract description 51
- 238000009841 combustion method Methods 0.000 title claims description 18
- 230000003197 catalytic effect Effects 0.000 title abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 185
- 239000007789 gas Substances 0.000 claims abstract description 63
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 54
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 53
- 239000000567 combustion gas Substances 0.000 claims abstract description 25
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims abstract 5
- 229910001882 dioxygen Inorganic materials 0.000 claims abstract 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 127
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 115
- 239000010410 layer Substances 0.000 claims description 24
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 23
- 239000004480 active ingredient Substances 0.000 claims description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 22
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 229910003445 palladium oxide Inorganic materials 0.000 claims description 9
- 229910003446 platinum oxide Inorganic materials 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 4
- 229910052779 Neodymium Inorganic materials 0.000 claims description 4
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 4
- 229910052788 barium Inorganic materials 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052746 lanthanum Inorganic materials 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 4
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052712 strontium Inorganic materials 0.000 claims description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 239000011247 coating layer Substances 0.000 claims 2
- 239000012041 precatalyst Substances 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 17
- 239000008246 gaseous mixture Substances 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 14
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 14
- 239000000843 powder Substances 0.000 description 13
- 238000002474 experimental method Methods 0.000 description 9
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 7
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 6
- 229910044991 metal oxide Inorganic materials 0.000 description 6
- 150000004706 metal oxides Chemical class 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- GPNDARIEYHPYAY-UHFFFAOYSA-N palladium(ii) nitrate Chemical compound [Pd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O GPNDARIEYHPYAY-UHFFFAOYSA-N 0.000 description 5
- 239000003870 refractory metal Substances 0.000 description 5
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 4
- 238000007084 catalytic combustion reaction Methods 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- 239000003063 flame retardant Substances 0.000 description 4
- 239000003345 natural gas Substances 0.000 description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 description 4
- 238000010248 power generation Methods 0.000 description 4
- 239000001294 propane Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- FCUFAHVIZMPWGD-UHFFFAOYSA-N [O-][N+](=O)[Pt](N)(N)[N+]([O-])=O Chemical compound [O-][N+](=O)[Pt](N)(N)[N+]([O-])=O FCUFAHVIZMPWGD-UHFFFAOYSA-N 0.000 description 2
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000395 magnesium oxide Substances 0.000 description 2
- 239000011268 mixed slurry Substances 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- IATRAKWUXMZMIY-UHFFFAOYSA-N strontium oxide Chemical compound [O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 description 2
- 238000000859 sublimation Methods 0.000 description 2
- 230000008022 sublimation Effects 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- -1 cobalt and nickel Chemical compound 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000953 kanthal Inorganic materials 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- JRTYPQGPARWINR-UHFFFAOYSA-N palladium platinum Chemical compound [Pd].[Pt] JRTYPQGPARWINR-UHFFFAOYSA-N 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910003447 praseodymium oxide Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- JUWGUJSXVOBPHP-UHFFFAOYSA-B titanium(4+);tetraphosphate Chemical compound [Ti+4].[Ti+4].[Ti+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O JUWGUJSXVOBPHP-UHFFFAOYSA-B 0.000 description 1
Landscapes
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
Description
【発明の詳細な説明】
〈産業上の利用分野〉
本発明はメタン系燃料特にメタンを主成分とし、エタン
、プロパン、ブタン等の低級炭化水素からなる天然ガス
を触媒上で接触燃焼せしめ、窒素酸化物（以下、ＮＯｘ
という）、−酸化炭素（以下、ＣＯという）、未燃焼炭
化水素（以下、ＵＨＣという）等の有害成分を実質的に
含有しないクリーンな燃焼ガスを得、その熱量を各種の
一部エネルギー源として、特に発電用ガスタービンに用
いるための燃焼用触媒システムおよびそれを用いた燃焼
方法に関するものである。[Detailed Description of the Invention] <Industrial Application Field> The present invention catalytically burns methane-based fuel, particularly natural gas containing methane as the main component and lower hydrocarbons such as ethane, propane, and butane, on a catalyst, and Oxide (hereinafter referred to as NOx
), - Obtain clean combustion gas that does not substantially contain harmful components such as carbon oxide (hereinafter referred to as CO) and unburned hydrocarbons (hereinafter referred to as UHC), and use the resulting heat as a partial energy source for various types. In particular, the present invention relates to a combustion catalyst system for use in a gas turbine for power generation and a combustion method using the same.
〈従来の技術〉
燃料を燃焼範囲に入らない低い１１度で空気と混合した
希薄混合気体を触媒層へ導入し、触媒上で接触燃焼せし
め高温の燃焼ガスをえるための触媒燃焼システムは公知
である。<Prior art> A catalytic combustion system is known in which a dilute mixture of fuel and air at a temperature of 11 degrees below the combustion range is introduced into a catalyst layer and catalytically combusted on the catalyst to obtain high-temperature combustion gas. be.
さらに、かかる触媒燃焼システムを用いて、たとえば６
００℃から１５００℃の燃焼ガスをえる場合、たとえば
酸素源に空気を用いてもＮＯｘがほとんどないしは全く
発生することがなく、またＣ０９ｔＪＨｃも実質的に含
有しないものとしてえられることもよ（知られるところ
である。Furthermore, using such a catalytic combustion system, e.g.
When obtaining combustion gas between 00°C and 1500°C, for example, even if air is used as an oxygen source, little or no NOx is generated, and it is also possible to obtain a combustion gas that does not substantially contain CO9tJHc. By the way.
このクリーンな高温燃焼ガスを利用し、熱または動力を
えるシステムは各種提案され、一般産業排ガスの処理お
よび熱動力回収システムはすでに実用化されるに至って
いる。Various systems have been proposed that utilize this clean, high-temperature combustion gas to generate heat or power, and general industrial exhaust gas treatment and thermal power recovery systems have already been put into practical use.
また近年になり、高まるＮＯｘ規制への対応から、発電
用ガスタービンなどの一部勅力源用としてこの高温燃焼
ガスを利用する研究がなされるようになりつつある。In recent years, in response to increasing NOx regulations, research has begun to be conducted on the use of this high-temperature combustion gas as a power source for some power generation gas turbines and the like.
これらの接触燃焼システムには、アルミナ、ジルコニア
等の耐火性金属酸化物と、触媒活性成分である白金、パ
ラジウム、ロジウム等の貴金属あるいはコバルト、ニッ
ケル等の卑金属の酸化物、さらにはＬａＣ００１３等の
複合酸化物とをモノリス型担体に担持せしめた触媒体等
が提案されている。These catalytic combustion systems use composites such as refractory metal oxides such as alumina and zirconia, oxides of noble metals such as platinum, palladium, and rhodium, or base metals such as cobalt and nickel, which are catalytic active components, and even LaC0013. Catalysts in which oxides are supported on monolithic carriers have been proposed.
〈本発明が解決しようとする問題点〉
上記の如き触媒系を用い、ガスタービン等の一次動力源
として利用するシステムにおいては、タービンの特性上
触媒の使用条件は、５〜３０気圧のもとて１０００〜１
３００℃の高温に達せしめるのが通常であり、ガスター
ビンの効率向上のため、さらに高温、高圧になる傾向に
ある。<Problems to be Solved by the Present Invention> In a system using the catalyst system as described above and used as a primary power source such as a gas turbine, the catalyst is used under conditions of 5 to 30 atmospheres due to the characteristics of the turbine. Te1000~1
It is normal to reach a high temperature of 300°C, and in order to improve the efficiency of gas turbines, there is a trend towards even higher temperatures and pressures.
かかる条件下で、触媒を使用すると通常の触媒は高温の
ために急速に劣化し更にＲ悪の場合は触媒担体がメルト
ダウンし、飛散し、タービンのブレードなどを損傷して
しまう可能性がある。When a catalyst is used under such conditions, a normal catalyst deteriorates rapidly due to the high temperature, and in the worst case, the catalyst carrier may melt down and fly off, damaging turbine blades, etc. .
上記の如き触媒の劣化、損傷を避け、同等の目的をえる
燃焼方法として、触媒層において燃料の一部を燃焼させ
、２次燃焼が誘発される温度にまでガス温度を上昇せし
め、次いで触ｖＡ層後方で残存未燃燃料を２次燃焼させ
るか、または必要であれば２次燃料を導入して残存未燃
燃料と新たに添加した２次燃料を、２次的に燃焼させて
目的とする温度、あるいはそれ以上の温度のクリーンな
燃焼ガスをえる燃焼方法が見出された。As a combustion method that avoids deterioration and damage to the catalyst as described above and achieves the same purpose, a part of the fuel is combusted in the catalyst layer, the gas temperature is raised to a temperature that induces secondary combustion, and then the gas temperature is increased to a temperature that induces secondary combustion. The remaining unburned fuel is secondaryly combusted behind the layer, or if necessary, secondary fuel is introduced and the remaining unburned fuel and newly added secondary fuel are combusted secondarily to achieve the desired purpose. A combustion method has been discovered that produces clean combustion gases at or above temperatures.
この場合、触媒層での燃焼は、ガス温度を２次燃焼が誘
発される温度にまで上昇させるのを目的としており必ず
しも触媒層で完全燃焼させる必要はなく、２次燃焼が誘
発される温度以上にガス温度が到達すれば触媒の劣化、
損傷を避けるためにも、また、２次燃焼を安定して維持
させるためにも、触ｔＲ層中でより高温にする必要はな
く、むしろ残存未燃燃料が多い方が好ましい。In this case, the purpose of combustion in the catalyst layer is to raise the gas temperature to a temperature that induces secondary combustion, and it is not necessarily necessary to completely burn the gas in the catalyst layer, but to raise the gas temperature to a temperature that induces secondary combustion. If the gas temperature reaches , the catalyst will deteriorate,
In order to avoid damage and to maintain stable secondary combustion, it is not necessary to increase the temperature in the tR layer, but rather it is preferable that there be a large amount of remaining unburned fuel.
燃料は目的とする温度がえられる仝司を触媒層へ導入し
、一部を燃焼させて昇温し、ついで残存未燃燃料を２次
燃焼させてもよいが、燃料の一部を残しておき、これを
２次燃料として触媒層後方から導入して残存未燃燃料と
合わせて２次燃焼させてもよい。この場合触媒層温度を
必要以上の高温とすることも避けられ、触媒の劣化、損
傷を避けることが出来、より好ましい。It is also possible to introduce a fuel that can obtain the desired temperature into the catalyst layer, combust a portion of it to raise the temperature, and then perform secondary combustion of the remaining unburned fuel. This may be introduced as a secondary fuel from behind the catalyst layer and combined with the remaining unburnt fuel for secondary combustion. In this case, it is possible to avoid setting the temperature of the catalyst layer higher than necessary, and it is possible to avoid deterioration and damage to the catalyst, which is more preferable.
ここで２次燃焼を誘発させるのに必要な温度は、燃料の
種類、残存燃料濃度（理論断熱燃焼ガス温度）、線速等
によって決まるが、燃料の種類により大幅に異なる。The temperature required to induce secondary combustion here is determined by the type of fuel, residual fuel concentration (theoretical adiabatic combustion gas temperature), linear velocity, etc., and varies significantly depending on the type of fuel.
すなわち、プロパン、軽油等の易燃性の燃料の場合は通
常の使用条件下では約７００℃程痕でも十分であるが、
難燃性のメタン、あるいはメタンを主成分とする天然ガ
スを燃料とする場合は使用条件によって異なるものの７
５０〜１０００℃の高温が必要である。又、ガスタービ
ンとしての機能を有するためには、圧力損失を小ざくし
、燃焼器を小容量に保って、燃焼負荷率を大きくするこ
とが求められており、触媒容量はできるだけ小さくする
必要があり、その結果触媒層入口の線速は５〜４０ｍ／
秒（５００℃換算）、空間速度は８０〜６００万（時間
）と従来の触媒反応にはない、非常に過酷な条件で使用
されることになる。In other words, in the case of easily flammable fuels such as propane and light oil, a temperature of about 700°C is sufficient under normal usage conditions;
When using flame-retardant methane or natural gas whose main component is methane, the fuel consumption varies depending on the conditions of use.7
High temperatures of 50-1000°C are required. In addition, in order to function as a gas turbine, it is necessary to minimize pressure loss, keep the combustor capacity small, and increase the combustion load rate, and the catalyst capacity must be as small as possible. As a result, the linear velocity at the inlet of the catalyst layer is 5 to 40 m/
seconds (calculated at 500°C), and the space velocity is 800 to 600,000 hours (hours), which means that it will be used under extremely harsh conditions that are not found in conventional catalytic reactions.
かかる高圧の条件下で、可燃性ガス、特にメタン等の難
燃性ガスを触媒層において燃料を一部接触燃焼せしめ、
２次燃焼が誘発される温度にまでガス温度を上昇せしめ
、次いで接触層後方で残存未燃燃料を２次燃焼させるか
、または必要であれば２次燃料を尋人して残存未燃燃料
と新たに添加して２次燃料を、２次的に燃焼させる２段
燃焼方法により完全燃焼せしめようとする場合、加圧に
よる燃料流口の増大に伴い、触媒での燃焼効率が大きく
低下し、いまだ実用的に完成された触媒体を得るには至
っていない。Under such high pressure conditions, combustible gas, especially flame retardant gas such as methane, is partially catalytically burned in the catalyst layer,
The gas temperature is raised to a temperature that induces secondary combustion, and then the remaining unburned fuel is subjected to secondary combustion behind the contact layer, or if necessary, the secondary fuel is intermixed with the remaining unburned fuel. When trying to achieve complete combustion using a two-stage combustion method in which newly added secondary fuel is burned secondarily, the combustion efficiency at the catalyst decreases significantly due to the increase in the fuel flow opening due to pressurization. A practically completed catalyst body has not yet been obtained.
く本発明の目的〉
そこで本発明の目的は、上記の如き高圧高線速下のガス
タービンの実使用条件下においても、より小さい触媒容
量で難燃性のメタン系燃料をより低温で着火せしめ、燃
焼ガス温度を７５０〜１０００℃の温度にまで上界せし
め、かつ耐久性を有し、ＣＯ，ＮＯｘ 、Ｕｌ−ＩＣ等
の有害成分を実質的に含有しない燃焼用触媒システムを
提供しもってその有効な利用方法を提供することにある
。Therefore, the object of the present invention is to ignite flame-retardant methane fuel at a lower temperature with a smaller catalyst capacity even under the above-mentioned conditions of actual use of a gas turbine under high pressure and high linear velocity. , by providing a combustion catalyst system that can raise the combustion gas temperature to a temperature of 750 to 1000°C, has durability, and does not substantially contain harmful components such as CO, NOx, and Ul-IC. The purpose is to provide effective usage methods.
く問題点を解決するための手段〉
かかる目的を達成するために、本発明者らは可燃性ガス
のなかで最も難燃性であるメタンを用い、常圧から高圧
にわたる各種の条件下での接触燃焼に関して検討した。Means for Solving Problems〉 In order to achieve the above object, the present inventors used methane, which is the most flame-retardant among combustible gases, and conducted experiments under various conditions ranging from normal pressure to high pressure. We investigated catalytic combustion.
その結果、メタンの燃焼反応はガス入口側、すなわち前
段部の低温域触媒においては、主に触媒表面上での不均
一反応に依存しており、一方ガス出口側すなわち後段部
の０温域においては、主として気相中での均一反応に依
存しているという知見を得た。つまり同一線速下では加
圧によるガス密度ならびにガス流量の増大に伴い、前段
部の触媒表面上での不均一反応は、燃料ガスの物質移動
による拡散律速から、触媒表面上での反応律速に移行し
、燃焼効率の大きな低下を招くものであり、一方接段部
の気相中での燃焼反応は、燃焼効率の向上を招くもので
あることを見い出した。As a result, the combustion reaction of methane mainly depends on the heterogeneous reaction on the catalyst surface on the gas inlet side, that is, in the low-temperature region catalyst in the first stage, while on the gas outlet side, that is, in the zero-temperature region in the second stage. It was found that the reaction mainly depends on a homogeneous reaction in the gas phase. In other words, under the same linear velocity, as the gas density and gas flow rate increase due to pressurization, the heterogeneous reaction on the catalyst surface in the front stage changes from diffusion-limited by mass transfer of fuel gas to reaction-limited on the catalyst surface. It has been found that the combustion reaction in the gas phase at the stage contact part, on the other hand, leads to an improvement in combustion efficiency.
そして、上記のようなメタンの燃焼反応に適する触媒を
鋭意検討した結果、本発明を完成するに至った。As a result of extensive research into catalysts suitable for the combustion reaction of methane as described above, the present invention was completed.
すなわち、本発明の燃焼用触媒システムは複層の触媒層
に分けられメタン系燃料と分子状酸素含有ガスからなる
高圧高線速の可燃性混合ガスの流れに対して、ガス入口
側にパラジウム、白金およびニッケル酸化物を活性成分
とする前段触媒層、およびガス出口側に白金を活性成分
とする、あるいは白金およびパラジウムを活性成分とす
る後段触媒層を組合せた触媒システムからなり、該触媒
システムに担持されたパラジウムおよび白金の合計の全
担持量が担体容積１１あたり１０〜１００ｑであること
を特徴とし、前段触媒層で比較的低温から着火せしめ、
燃焼ガス温度を７５０〜１０００℃まで上昇させうるよ
うに各々最適に設計して成るものであり、かつ１０００
℃を超える高温にはならないようにして成るものである
。That is, the combustion catalyst system of the present invention is divided into multiple catalyst layers, and palladium, palladium, It consists of a catalyst system that combines a front stage catalyst layer containing platinum and nickel oxide as active components, and a rear stage catalyst layer on the gas outlet side that has platinum as an active component or platinum and palladium as active components. It is characterized in that the total amount of supported palladium and platinum is 10 to 100 q per 11 carrier volumes, and ignition is performed at a relatively low temperature in the front catalyst layer,
Each of them is optimally designed to raise the combustion gas temperature to 750 to 1000°C, and
It is constructed in such a way that it does not reach high temperatures exceeding ℃.
その結果メタンの燃焼反応に対する触媒活性が大幅に向
上して加圧下において燃焼性能の低下を１ｕく空間速度
の増大（接触時間の短縮）、入口高線速の影響に対して
も２段燃焼方法により完全燃焼せしめることが可能にな
り、触媒古註を小さくして燃焼負荷率を向上出来、実際
のガスタービン燃焼器への実用化が可能となることを見
い出したのである。As a result, the catalytic activity for the methane combustion reaction has been significantly improved, reducing the deterioration of combustion performance by 1 u under pressure, increasing the space velocity (shortening the contact time), and using a two-stage combustion method to overcome the effects of high linear velocity at the inlet. They discovered that it is possible to achieve complete combustion, reduce the size of the catalyst, improve the combustion load factor, and make it possible to put it into practical use in actual gas turbine combustors.
さらに本発明における燃焼用触媒システムを具体的に説
明する。Furthermore, the combustion catalyst system according to the present invention will be specifically explained.
パラジウムを活性主成分とする触媒は特にメタンの低温
着火性にすぐれ、かつ１０００℃程度の高温での耐熱性
にもすぐれた触媒として知られる。Catalysts containing palladium as the main active component are known to have particularly excellent low-temperature ignitability of methane and excellent heat resistance at high temperatures of about 1000°C.
しかしながら、従来のパラジウムを活性成分とする触媒
を本発明目的に使用した場合、触媒層入日付近において
は５００℃以下の温度で高濃度の酸素にさらされるため
パラジウムは酸化されメタンの着火性能を失い、また一
方、触媒層出口付近の高温域においては、パラジウムの
酸化状態が変化することによると考えられる理由から触
媒による燃焼反応は抑制され燃焼ガス温度は実質７５０
℃以上の高温には上昇しないという欠点がある。However, when a conventional catalyst containing palladium as an active ingredient is used for the purpose of the present invention, the catalyst layer is exposed to high concentrations of oxygen at temperatures below 500°C near sunrise, so palladium is oxidized and impairs methane ignition performance. On the other hand, in the high-temperature region near the outlet of the catalyst layer, the combustion reaction by the catalyst is suppressed, presumably due to a change in the oxidation state of palladium, and the combustion gas temperature is essentially 750℃.
It has the disadvantage that it cannot rise to high temperatures above ℃.
これに対し、本発明によれば燃焼用触媒システムのガス
入口側ｔなわち前段触ｖｉ、層は主としてパラジウムを
活性成分としたものであり、白金およびニッケル酸化物
がさらに活性成分として添加されている。つまり少呈の
白金の存在により、パラジウムの酸化物化によるメタン
着火性能の低下が防止され、長時間に万り低温着火性能
を維持しつづけることができるとともに、ニッケルが酸
化物として存在することによりパラジウムに安定して空
気から酸素が供給されるため燃焼ガス温度を高圧、高線
速下で６００〜９００℃まで昇温せしめ、続いて存在す
る後段触媒層での燃焼反応を容易に開始せしめ得るもの
である。On the other hand, according to the present invention, the gas inlet side (t), that is, the first stage (vi) layer of the combustion catalyst system mainly contains palladium as an active ingredient, and platinum and nickel oxide are further added as active ingredients. There is. In other words, the presence of a small amount of platinum prevents the deterioration of methane ignition performance due to the formation of palladium into oxides, making it possible to maintain low-temperature ignition performance for a long time. Because oxygen is stably supplied from the air, the temperature of the combustion gas can be raised to 600 to 900°C under high pressure and high linear velocity, and then the combustion reaction in the subsequent catalyst layer can be easily started. It is.
特に、低温度域（３００〜７００℃）における燃焼反応
を十分に行なわせるために、パラジウム、白金およびニ
ッケル酸化物を最適に組合せることが好ましく、前段触
媒層を２層に分け（の萌半部がパラジウム、白金および
ニッケル酸化物を活性成分とする触媒層、後半部（中段
触媒層）がパラジウムおよび白金を活性成分とする触媒
層、あるいはパラジウムおよびニッケル酸化物を活性成
分とする触媒層の組合けを選７Ｓこともできる。In particular, in order to sufficiently carry out the combustion reaction in the low temperature range (300 to 700 degrees Celsius), it is preferable to optimally combine palladium, platinum and nickel oxides, and the front catalyst layer is divided into two layers (one half and one half). The second half is a catalyst layer containing palladium, platinum and nickel oxide as active ingredients, and the second half (middle catalyst layer) is a catalyst layer containing palladium and platinum as active ingredients, or a catalyst layer containing palladium and nickel oxide as active ingredients. You can also select a combination of 7S.
一方、燃焼用触媒システムのガス出口側すなわち後段触
媒層は主として白金を活性成分としたものであり、白金
にＪ：っで燃焼はさらに促進されて燃焼ガスは７５０〜
１０００℃の温度に到らしめることが可能になる。触媒
層中において高圧メタン系燃料を完全燃焼せしめようと
すると、触媒温度は多くの場合１０００℃以上の高温に
なり、白金が酸化されてＰｔ０１３になり昇華飛散され
る。そのためパラジウムを共存せしめ白金の昇華飛散を
防止抑制する必要があり、白金およびパラジウムを活性
成分とする触媒が用いられるが触媒層後方でも一部燃料
を燃焼せしめて完全燃焼に到る２段燃焼方法の場合、触
媒温度は１０００℃以下に抑制することができ、白金の
昇華飛散による活性成分へ及ぼす影響は小さくなるので
白金およびパラジウムを活性成分とする触Ｉｓ層ととも
に白金のみを活性成分とする触媒層を用いることも可能
である。On the other hand, the gas outlet side of the combustion catalyst system, that is, the latter catalyst layer, mainly contains platinum as an active ingredient.
It becomes possible to reach a temperature of 1000°C. When attempting to completely burn high-pressure methane-based fuel in the catalyst layer, the catalyst temperature often reaches a high temperature of 1000° C. or higher, and platinum is oxidized to become Pt013, which is sublimated and scattered. Therefore, it is necessary to coexist with palladium to prevent sublimation and scattering of platinum, and a catalyst containing platinum and palladium as active components is used, but a two-stage combustion method in which part of the fuel is combusted even behind the catalyst layer to reach complete combustion. In this case, the catalyst temperature can be suppressed to 1000°C or less, and the effect of sublimation and scattering of platinum on the active components is small. It is also possible to use layers.
以上のように本発明になる触媒システｌいはそれぞれの
貴金属の特性を生かしであるいは組合せて２段あるいは
３段構成からなることを特徴としており、メタン系燃料
を高圧、高線速下で３００〜４００℃の低温で着火せし
め、７５０゛〜１０００℃の燃焼ガス温度を１ｑるため
の燃焼活性を有し、かつ１０００℃以上の耐熱性を有し
ているのである。As described above, the catalyst system according to the present invention is characterized by having a two-stage or three-stage configuration by taking advantage of the characteristics of each precious metal or by combining them. It can be ignited at a low temperature of ~400°C, has combustion activity to lower the combustion gas temperature by 1q from 750°C to 1000°C, and has heat resistance of 1000°C or higher.
しかしながら、パラジウムのみを活性成分とづる触媒は
、前）本のように燃焼経過とともに着火性能を失ない、
又、燃焼ガス温度は、実質に７５０℃以上の高温には上
昇しないという欠点がある。However, catalysts containing only palladium as the active ingredient do not lose their ignition performance as the combustion progresses, as in the previous book.
Another disadvantage is that the combustion gas temperature does not substantially rise to a high temperature of 750° C. or higher.
白金のみを活性成分とする触媒は燃料がメタンや天然ガ
スのようなメタン系燃料の場合には高圧、高線速燃料条
件下でも燃焼活性は優れているが３００〜４００℃では
着火不能であり、実質的に５００℃以上の着火温度が必
要となり好ましくない。A catalyst containing only platinum as an active component has excellent combustion activity even under high pressure and high linear velocity fuel conditions when the fuel is methane or methane-based fuel such as natural gas, but cannot ignite at 300 to 400°C. , an ignition temperature of substantially 500° C. or higher is required, which is not preferable.
また、パラジウム−白金−ニッケル酸化物あるいはパラ
ジウム−白金系触媒では充分な着火性能は有するが、燃
焼ガス温度を高圧、高線速燃焼条件下で２次燃焼が誘発
される温度以上にすることはできない。Furthermore, although palladium-platinum-nickel oxide or palladium-platinum catalysts have sufficient ignition performance, it is difficult to raise the combustion gas temperature above the temperature at which secondary combustion is induced under high pressure and high linear velocity combustion conditions. Can not.
以上のように１段構成のものはそれぞれ欠点を有してお
り、特に高圧燃焼条件においては、実用触媒とはなりえ
ず、好ましくない。As described above, each of the one-stage configurations has drawbacks and cannot be used as a practical catalyst, especially under high-pressure combustion conditions, and is therefore undesirable.
前段部の触媒（前段触媒層および中段触媒層）の白金族
元素の担持量は担体容Ｖｉ１ｊ！あたり２０〜１００ｇ
好ましくは３０〜６０ａであり、白金に対するパラジウ
ムの担持比は１〜２５、好ましくは２〜１０である。ま
たニッケル酸化物の担持量はパラジウムに安定して空気
から酸素を供給せしめるためには担体容積１１あたり１
０〜１５０ｇが適当であり、好ましくは５０〜１２０ｇ
である。後段部の触媒の白金族元素の担持量は担体容積
１１あたり１０〜８０ｇ、好ましくは２０〜５０（＋で
白金とパラジウムが共存する場合には、白金に対するパ
ラジウムの担持比は０．１〜１０、好ましくは０．２〜
５である。The amount of platinum group elements supported in the front catalyst (first stage catalyst layer and middle stage catalyst layer) is determined by the carrier volume Vi1j! 20-100g per
Preferably it is 30-60a, and the supporting ratio of palladium to platinum is 1-25, preferably 2-10. In addition, the amount of nickel oxide supported is 1/11 of the carrier volume in order to stably supply oxygen from the air to palladium.
0-150g is appropriate, preferably 50-120g
It is. The amount of platinum group elements supported in the catalyst in the latter stage is 10 to 80 g per carrier volume 11, preferably 20 to 50 (+, when platinum and palladium coexist, the supporting ratio of palladium to platinum is 0.1 to 10 , preferably 0.2~
It is 5.
該触媒体は前段から後段にかけて複数段に分けて別個に
調製し、各触媒を直結してまたは空間を設けて設置して
もよいしあるいは一体物の触媒体として完全触媒として
もよい。The catalyst body may be prepared separately from a plurality of stages from the first stage to the second stage, and each catalyst may be directly connected or installed with a space provided, or it may be a complete catalyst as an integrated catalyst body.
複数段に分けて別個に調製した場合、白金族元素の担持
ｍが担体古註１１あたり１０（＋を下回る触媒が存在し
ても、完成した触媒体として白金族元素の全担持世が１
０（］以上であれば、当然使用することが可能である。When prepared separately in multiple stages, even if there is a catalyst in which the platinum group element supported m is less than 10 (+) per carrier, the total supported platinum group element m as a completed catalyst is 1
If it is 0(] or more, it can of course be used.
白金族元素の全担持量が１０ｏを下回る場合は加圧によ
るガス密度および流量の増大に伴い、燃焼せしめようと
するメタン分子数に対して活性物質の量が不足すること
になる。そのためメタンの着火温度が本発明の前段部の
触媒の着火温度である３００〜４００℃に比較して轟く
なり、予備燃焼のためにパイロットバーナーが必要とな
ると共に、着火せしめるためパイロットバーナ一部での
予備燃焼の比率が高くなりＮＯｘの発生ム１が増大する
。If the total amount of platinum group elements supported is less than 10 degrees, the amount of active substance will be insufficient relative to the number of methane molecules to be combusted as the gas density and flow rate increase due to pressurization. Therefore, the ignition temperature of methane is higher than the ignition temperature of the catalyst in the front stage of the present invention, which is 300 to 400°C, and a pilot burner is required for preliminary combustion, and a part of the pilot burner is used to ignite the methane. The ratio of pre-combustion increases, and the amount of NOx generated increases.
さらにたとえ着火しても、その燃焼活性は低く、燃料の
吹き扱けが多くなり、燃焼ガス温度が十分に上昇しない
ためあとに続く触媒後段部での燃焼反応に至らしめるこ
とが困難となる。加えて、後段部触媒も低活性のため、
燃焼は不十分で燃料の吹き扱けが非常に多く、２次燃焼
が誘発される温度にまでガス温度を上昇せしめることも
非常に困難となる。従って、白金族元素の全担持量が１
０ｑ以下の触媒体が常圧下では高活性であっても、加圧
下では十分な燃焼活性を右さない。Furthermore, even if it ignites, its combustion activity is low, the fuel is blown over a lot, and the temperature of the combustion gas does not rise sufficiently, making it difficult to cause a combustion reaction in the subsequent stage of the catalyst. In addition, the downstream catalyst also has low activity, so
Combustion is insufficient and there is a large amount of fuel being blown away, making it extremely difficult to raise the gas temperature to a temperature that induces secondary combustion. Therefore, the total amount of platinum group elements supported is 1
Even if a catalyst having 0q or less has high activity under normal pressure, it does not exhibit sufficient combustion activity under pressurized conditions.
一方、白金族元素の全担持量が１００（Ｉを越える場合
には、分散性が低下するものの活性物質の増加による燃
焼活性が向上し燃焼ガス温度を１０００℃以下に抑制す
ることはできず、急激に活性低下をきたすとともに触媒
が非常に高価となるので好ましくない。On the other hand, when the total amount of platinum group elements supported exceeds 100 (I), although the dispersibility decreases, the combustion activity increases due to the increase in active substances, and the combustion gas temperature cannot be suppressed to below 1000°C. This is not preferable because it causes a sudden decrease in activity and makes the catalyst very expensive.
ニッケル酸化物の担持量が担体容積１１あたり１０ｑを
下回る場合はパラジウムへの空気からの酸素の供給が不
十分なため前段部触媒の燃焼活性は十分に発揮されず、
１５００を越える場合は分散性が悪くなり、燃焼活性の
低下を招くものである。If the amount of nickel oxide supported is less than 10q per carrier volume 11, the combustion activity of the front stage catalyst will not be sufficiently exerted due to insufficient supply of oxygen from air to palladium.
When it exceeds 1500, dispersibility deteriorates, leading to a decrease in combustion activity.
触媒の担体としては、圧力損失を少くする目的から、モ
ノリスタイプのものが好ましい。モノリス担体は通常当
該分野で使用されるものであればいずれも使用可能であ
り、とくにコージェライト、ムライト、α−アルミナ、
ジルコニア、チタニア、リン酸チタン、アルミニウムチ
タネート、ベタライト、スボジュメン、アルミノシリケ
ート、ケイ酸マグネシウム、ジルコニア−スピネル、ジ
ルコン−ムライト、炭化ケイ素、窒化ケイ素などの耐熱
性セラミック質のものやカンタル、フエクラロイ等の金
属製のものが使用される。As the catalyst carrier, a monolith type carrier is preferable for the purpose of reducing pressure loss. Any monolithic support commonly used in the field can be used, especially cordierite, mullite, α-alumina,
Heat-resistant ceramics such as zirconia, titania, titanium phosphate, aluminum titanate, betalite, subodumene, aluminosilicate, magnesium silicate, zirconia-spinel, zircon-mullite, silicon carbide, silicon nitride, and metals such as Kanthal and Feclaroy. manufactured products are used.
モノリス担体のセルサイズは、燃焼効率が低下しない限
り大きいものが好ましく、各触媒層は同一セルサイズで
もよいし、また異なるセルサイズのものを組合Ｖて用い
てもよく、通常−平方インチあたり４０〜４００セルの
ものが用いられる。The cell size of the monolithic carrier is preferably large as long as the combustion efficiency is not reduced; each catalyst layer may have the same cell size, or different cell sizes may be used in combination. ~400 cells are used.
全触媒層長は特に使用される入口線速によって異なるが
、圧力損失を少くする必要から通常５０〜３００履が採
用され、各層の長さも圧力、燃料濃度、入口線速、入口
温度等の使用条件によって最適に選択されるが、通常各
層共１０〜２００ｍ＋が採用される。The total catalyst layer length varies depending on the inlet linear velocity used, but 50 to 300 layers is usually adopted due to the need to reduce pressure loss, and the length of each layer also depends on the pressure, fuel concentration, inlet linear velocity, inlet temperature, etc. Although it is optimally selected depending on the conditions, 10 to 200 m+ is usually adopted for each layer.
白金族元素としては白金、パラジウムが特に優れるが、
その他ロジウム、イリジウム等を添加してもよい。Platinum and palladium are particularly good as platinum group elements, but
In addition, rhodium, iridium, etc. may be added.
また、ニッケル、コバルト、鉄、クロム等の金属酸化物
やＣｏＮｉ０１３．１ａＣＯＯ１３、ＣｕＣｒ０１ａ等
の複合酸化物も白金族元素と併用することによって活性
物質としての効果を発揮する。In addition, metal oxides such as nickel, cobalt, iron, and chromium, and composite oxides such as CoNi013.1aCOO13 and CuCr01a, also exhibit effects as active substances when used in combination with platinum group elements.
これらの活性成分とアルミナを前記モノリス担体に担持
して触媒化する。またシリカ−アルミナ、マグネシア、
ヂタニア、ジルコニア、シリカ−マグネシアなどの耐火
性金属酸化物も用いることができる。These active ingredients and alumina are supported on the monolithic carrier and catalyzed. Also silica-alumina, magnesia,
Refractory metal oxides such as ditania, zirconia, silica-magnesia, etc. can also be used.
上記耐火性台ｍｓ化物は、バリウム、ストロンチウム等
のアルカリ土類金属酸化物、ランタン、ネオジム、セリ
ウム、プラセオジムなどの希土類金属酸化物あるいはシ
リカ酸化物を添加し安定化して用いると好ましい。The above-mentioned refractory MS compound is preferably stabilized by adding an alkaline earth metal oxide such as barium or strontium, a rare earth metal oxide such as lanthanum, neodymium, cerium, or praseodymium, or silica oxide.
特にアルミナの場合、ランタン、セリウム、サマリウム
、ネオジム、プラセオジム、カルシウム、ストロンチウ
ム、バリウムおよびシリカよりなる群から選ばれた少な
くとも１種の酸化物によって安定化されたものを用いる
とより好ましい。In particular, in the case of alumina, it is more preferable to use one stabilized by at least one oxide selected from the group consisting of lanthanum, cerium, samarium, neodymium, praseodymium, calcium, strontium, barium and silica.
触媒成分の担持方法としては、耐火性金属酸化物をコー
ティングし、そのあと活性成分を水溶性の塩の形で含浸
せしめても良い、あるいはあらかじめ活性成分を耐火性
金属酸化物に担持又は混合して、その後モノリス担体に
担持しても良い。The catalyst component may be supported by coating the refractory metal oxide and then impregnating the active component in the form of a water-soluble salt, or by supporting or mixing the active component with the refractory metal oxide in advance. Then, it may be supported on a monolithic carrier.
水溶性塩としては、硝酸塩、硫酸塩、リンＦｉ塩、ハロ
ゲン化物、ジニトロジアミノ塩等がある。−例を挙げる
と、例えば硝酸パラジウム、塩化パラジウム、ジニトロ
ジアミノ白金、塩化白金酸等があり、これらの水溶液を
担体に含浸せしめて４００〜１０００℃、好ましくは６
００〜９００℃の温度で１〜２４時間、好ましくは２〜
６時間焼成することによりえられる。Examples of water-soluble salts include nitrates, sulfates, phosphorus Fi salts, halides, and dinitrodiamino salts. - Examples include palladium nitrate, palladium chloride, dinitrodiaminoplatinum, chloroplatinic acid, etc. A carrier is impregnated with an aqueous solution of these and heated at 400 to 1000°C, preferably 6
at a temperature of 00 to 900°C for 1 to 24 hours, preferably 2 to 24 hours.
Obtained by baking for 6 hours.
活性成分である白金については０．０１〜５ミクロンの
平均粒子径を有する白金ブラックとして活性耐火性金属
酸化物と共に担持せしめることもできる。Platinum, which is an active ingredient, can also be supported together with an active refractory metal oxide as platinum black having an average particle size of 0.01 to 5 microns.
またニッケル源としては硝酸ニッケル、塩化ニッケル、
酢酸ニッケルがあり、酸化ニッケルをそのまま用いても
よい。Nickel sources include nickel nitrate, nickel chloride,
Nickel acetate is available, and nickel oxide may also be used as is.
これら触媒成分は、使用条件に応じて入口側から出口側
にかけて最適に選定し組み合わせることによって本発明
は、ざらに効果的なものとなる。The present invention can be made more effective by optimally selecting and combining these catalyst components from the inlet side to the outlet side depending on the conditions of use.
本発明の燃焼用触媒システムに用いられる燃料はメタン
系燃料、特にメタンを主成分とし、エタン、プロパン、
ブタン等の低級炭化水素からなる天然ガスである。 ま
た活性汚泥処理などからの醗酵メタンや石炭ガス化によ
る低カロリーメタンガスなども本発明で用いられる燃料
である。またより易燃性のプロパン、軽油等も当然使用
することができる。The fuel used in the combustion catalyst system of the present invention is a methane-based fuel, in particular, methane is the main component, and ethane, propane,
It is a natural gas consisting of lower hydrocarbons such as butane. Further, fermented methane from activated sludge treatment and low-calorie methane gas from coal gasification are also fuels used in the present invention. Naturally, more flammable propane, light oil, etc. can also be used.
本発明の燃焼用触媒システムは、前述したように発電用
ガスタービンシステムに最適に組み込まれるものである
が、それ以外にも発電用ボイラ、熱回収用ボイラ、ガス
エンジンからのガスの後処理による熱回収、都市ガス暖
房など熱・動力回収を効率よく行うシステムに有利に組
み込まれる。The combustion catalyst system of the present invention can be optimally incorporated into a power generation gas turbine system as described above, but it can also be used in power generation boilers, heat recovery boilers, and after-treatment of gas from gas engines. It can be advantageously incorporated into systems that efficiently recover heat and power, such as heat recovery and city gas heating.
〈実施例〉
以下に本発明を実施例により、さらに詳細に説明するが
、本発明はこれらの実施例のみに限定されるものではな
い。<Examples> The present invention will be explained in more detail below with reference to Examples, but the present invention is not limited to these Examples.
実施例１
２００セル／平方インチの開孔部を右する直径２５．４
ｍ、ｌざ５０順のコージェライトハニカム担体に５重世
％の酸化ランタンを含有するアルミナ粉末と酸化ニッケ
ル粉末との混合スラリーを被覆処理し乾燥した後空気中
７００℃にて焼成して、担体容積１１あたり酸化ランタ
ン含有アルミナとして１００ｇ酸化ニッケルとして１０
０（＋を被覆担持せしめた。Example 1 Diameter 25.4 with 200 cells/inch square aperture
A mixed slurry of alumina powder and nickel oxide powder containing 5% lanthanum oxide was coated on a cordierite honeycomb carrier in the order of 50 mm and 50 mm, dried, and then fired at 700°C in air to form a carrier. 100g as lanthanum oxide-containing alumina per volume 11 10 as nickel oxide
0(+ was coated and supported.
次いで、これを硝酸パラジウムおよび塩化白金酸を含有
する水溶液に浸漬し、１５０℃で乾燥し、空気中９００
℃で５時間焼成し、担体容積１１あたりパラジウムとし
て５０ｇ１白金として１０ａ担持せしめて完成触媒を得
た。Next, this was immersed in an aqueous solution containing palladium nitrate and chloroplatinic acid, dried at 150°C, and heated at 900°C in air.
C. for 5 hours, and 50 g of palladium and 10 a of platinum were supported per 11 volumes of the carrier to obtain a completed catalyst.
実施例２
３８．８重量％の酸化ニッケルと２重量％酸化セリウム
および１重Ｒ％酸化ストロンチウムを含右するアルミナ
粉末に硝酸パラジウムと塩化白金酸を含有づる水溶液に
浸漬させて乾燥後空気中にて６００℃で３時間焼成しパ
ラジウムとして２４重Ｖ％、白金として３．９重σ％を
担持せしめた。Example 2 Alumina powder containing 38.8% by weight of nickel oxide, 2% by weight of cerium oxide, and 1% by weight of strontium oxide was immersed in an aqueous solution containing palladium nitrate and chloroplatinic acid, dried, and then exposed to air. The product was fired at 600° C. for 3 hours to support 24% by weight of palladium and 3.9% by weight of platinum.
次いでこのパラジウムおよび白金担持アルミナ粉末スラ
リーを２００セル／平方インチの開孔部を有する直径２
５．Ｉｌ＃ｌｌｌ！、長さ５０＃Ｉｌｌのムライトハニ
カム担体に被覆処理し乾燥したのち、空気中で７００℃
で５時間焼成することにより、担体容積１ｊ！あたりパ
ラジウムとして５０ｇ、白金として８０ Ｓｍ化ニッケ
ルとして８０ｇ担持せしめて完成触媒を得た。This palladium and platinum-supported alumina powder slurry was then poured into a 2 dia.
5. Il#llll! , coated on a mullite honeycomb carrier with a length of 50 #Ill, dried, and then heated at 700°C in air.
By firing for 5 hours, the carrier volume is reduced to 1j! A completed catalyst was obtained by supporting 50 g of palladium and 80 g of 80Sm nickel as platinum.
実施例３
実施例１と同様の担体に５重量％の酸化セリウムを含有
するアルミナ粉末と酸化ニッケル粉末との混合スラリー
を被覆処理し乾燥したのら、空気中で６００℃にて焼成
することにより担体容積１１あたり酸化セリウム含有ア
ルミナ粉末として１２０ｏ 、Ｍ化ニッケルとして８０
０を被覆担持せしめた。Example 3 A mixed slurry of alumina powder and nickel oxide powder containing 5% by weight of cerium oxide was coated on the same carrier as in Example 1, dried, and then fired at 600°C in air. 120o as cerium oxide-containing alumina powder and 80o as nickel Mide per carrier volume 11
0 was coated and supported.
次いで、これを硝酸パラジウムを含有する水溶液に浸漬
し、乾燥したのち空気中８００℃で５時間焼成し担体容
積１１あたりパラジウムとして２００担持せしめて完成
触媒を得た。Next, this was immersed in an aqueous solution containing palladium nitrate, dried, and then calcined in air at 800° C. for 5 hours to support 200 palladium per 11 volumes of the carrier to obtain a completed catalyst.
実施例４
４００セル／平方インチの開孔部を有する直径２５．４
＃ｌＩｌ、長さ５０＋ｍのコージェライ１〜ハニカム担
体に５重量％の酸化ランタンを含有するアルミナ粉末の
スラリーを実施例１と同様にして被覆処理し、担体容積
１１あたり酸化ランタン含有アルミナとして１００（Ｉ
を担持せしめた。Example 4 25.4 diameter with 400 cells/inch square aperture
A slurry of alumina powder containing 5 wt.
I was made to carry it.
次いで、硝酸パラジウムおよび硝酸ニッケルを含有する
水溶液に浸漬し、実施例３と同様にして担体容積１１あ
たりパラジウムとして３０ａ、１ｍ化ニッケルとして６
０ａ担持せしめて完成触媒を得た。Next, it was immersed in an aqueous solution containing palladium nitrate and nickel nitrate, and in the same manner as in Example 3, 30 a of palladium and 6 a of nickel per 1 m of carrier volume were added.
A completed catalyst was obtained by supporting Oa.
実施例５
実施例１と同様の担体に７重量％の酸化ランタンと３重
量％の酸化ネオジムを含右するアルミナ粉末のスラリー
を実施例１と同様にして担体容積１１あたり酸化ランタ
ンおよび酸化ネオジム含有アルミナとして１２０ｇ／ｌ
を被覆担持せしめた。Example 5 A slurry of alumina powder containing 7% by weight of lanthanum oxide and 3% by weight of neodymium oxide was added to the same carrier as in Example 1 in the same manner as in Example 1 to obtain a slurry containing lanthanum oxide and neodymium oxide per carrier volume of 11. 120g/l as alumina
was coated and supported.
次いで実施例２と同様にして担体容積１１あたリパラジ
ウムとして６０ｇ、白金として３０ａ担持せしめて完成
触媒を得た。Next, in the same manner as in Example 2, 60 g of lipalladium and 30 a of platinum were supported per carrier volume 11 to obtain a completed catalyst.
実施例６
実施例１と同様の担体に８重量％の酸化ランタンおよび
２重量％の酸化ケイ素を含右するアルミナ粉末のスラリ
ーを実施例１と同様にして担体容積１１あたり、酸化ラ
ンタンおよび酸化ケイ素含有アルミナとして１５０ｇを
被覆担持せしめた。Example 6 A slurry of alumina powder containing 8% by weight of lanthanum oxide and 2% by weight of silicon oxide was added to the same carrier as in Example 1 in the same manner as in Example 1 to obtain lanthanum oxide and silicon oxide per carrier volume of 11. 150 g of alumina was coated and supported.
次いで実施例２と同様にして担体容積１１あたリパラジ
ウムとして４０ｇ、白金として２０＋７担持せしめて完
成触媒を（りた。Next, in the same manner as in Example 2, 40 g of lipalladium and 20+7 platinum were supported per carrier volume 11 to obtain a completed catalyst.
実施例７
実施例１と同様の担体に実施例６と同様の酸化ランタン
および酸化ケイ素含有アルミナ粉末を１８０ｇ／ｌ被覆
担持せしめた。Example 7 The same carrier as in Example 1 was coated with the same lanthanum oxide and silicon oxide-containing alumina powder as in Example 6 at 180 g/l.
次いでこれをジニトロジアミノ白金を含有するｌｉｒｉ
Ｍ水溶液に浸漬し、乾燥したのち空気中で１１００℃に
て１０時間焼成し、担体容積１１あたり白金として２０
（Ｉ担持ぜしめて完成触媒を得た。This is then mixed with liri containing dinitrodiaminoplatinum.
After being immersed in an aqueous M solution and dried, it was calcined in air at 1100°C for 10 hours to obtain 20 platinum per 11 carrier volumes.
(A completed catalyst was obtained by supporting I.
実施例８
１００セル／平方インヂの開孔部を有する直径２５．４
ａｌ１１長さ５０ａｌｌのアルミニウムチタネートハニ
カム担体に４重量％の酸化バリウムと２重量％の酸化プ
ラセオジムを含有するアルミナ粉末のスラリーと平均０
．２ミクロンの粒径を有する白金ブ ′ラック粉末を
充分混合して被覆処理し、乾燥した後空気中で７００℃
にて５時間焼成して、担体容積１１あたり白金として３
０ａ担持せしめて完成触媒を得た。Example 8 Diameter 25.4 with 100 cells/square inch aperture
al11 A slurry of alumina powder containing 4% by weight barium oxide and 2% by weight praseodymium oxide on an aluminum titanate honeycomb carrier of length 50all and an average of 0
．． Platinum black powder with a particle size of 2 microns was thoroughly mixed and coated, dried and heated at 700°C in air.
3 as platinum per 11 carrier volume.
A completed catalyst was obtained by supporting Oa.
比較例１
実施例１と同様にして担体容積１１あたりパラジウムと
して５（］、白金として１ｇ担持せしめて完成触媒を得
た。Comparative Example 1 A completed catalyst was obtained in the same manner as in Example 1, by loading 5 (] of palladium and 1 g of platinum per 11 volumes of the carrier.
比較例２
実施例３と同様にして担体容積１１あたりパラジウムと
して２９１Ｍ化ニッケルとして８０ｏ担持せしめて完成
触媒を得た。Comparative Example 2 A completed catalyst was obtained in the same manner as in Example 3, by loading 80 degrees of 291M nickel as palladium per 11 volumes of the carrier.
比較例３
酸化ニッケルを含まない他は実施例４と同様にして担体
容積１１あたりパラジウムとして１０ａ担持せしめて完
成触媒を得た。Comparative Example 3 A completed catalyst was obtained in the same manner as in Example 4 except that nickel oxide was not included, and 10 a of palladium was supported per 11 volumes of the carrier.
比較例４
実施例６と同様にして担体容積１１あたり白金として２
（１，パラジウムとして４ｇ担持せしめて完成触媒を得
た。Comparative Example 4 In the same manner as in Example 6, 2 platinum was added per 11 carrier volumes.
(1. A completed catalyst was obtained by supporting 4g of palladium.
比較例５
実施例８と同様にして担体容積１１あたり白金として３
ｇ担持せしめて完成触媒を１７だ。Comparative Example 5 In the same manner as in Example 8, 3 platinum was added per 11 carrier volumes.
The finished catalyst with g supported is 17.
比較例６
実施例８と同様にして担体容積１１あたり白金として１
００ｇ担持せしめて完成触媒を得た。Comparative Example 6 In the same manner as in Example 8, 1 platinum was added per 11 carrier volumes.
A completed catalyst was obtained by supporting 00 g of the catalyst.
実施例９
十分に保温された円筒を燃焼器を用い、ガス入口側に実
施例１、次いで実施例３、ガス出口側に実施例８で得ら
れた触媒を充填し、入口温度３５０℃において３容量％
のメタンを含有するメタン−空気混合ガスを１５ａｔａ
の加圧下で１時間あたり１６７Ｎ況（ＳＴＰ）導入して
燃焼実験を行ない燃焼効率と触媒層出口温度を測定した
。この場合、触媒層入口線速は約２０ｍ ／秒（５００
℃換ｎ）であった。Example 9 Using a combustor, a sufficiently warm cylinder was filled with the catalyst obtained in Example 1 on the gas inlet side, followed by Example 3 on the gas outlet side, and the catalyst obtained in Example 8 on the gas outlet side. capacity%
15ata of methane-air mixed gas containing methane
A combustion experiment was conducted under a pressure of 167 N per hour (STP) and the combustion efficiency and catalyst layer outlet temperature were measured. In this case, the linear velocity at the inlet of the catalyst layer is approximately 20 m/s (500 m/s).
°C conversion n).
その結果、燃焼効率は約７３％で触媒層出口温度は約８
５０℃であった。As a result, the combustion efficiency was approximately 73%, and the catalyst bed outlet temperature was approximately 8.
The temperature was 50°C.
次いで、メタン濃度を４．１容量％にすると、燃焼効率
は１００％となり、ＵＨＯｌＣｏ、ＮＯＸを実質的に含
有しないクリーンな燃焼ガスかえられた。この場合、触
媒層後方１００Ｍの点の温度は約１３００℃に達してい
たが、触ＩＳＮ層出口温度は約９０５℃であった。Next, when the methane concentration was set to 4.1% by volume, the combustion efficiency became 100%, and a clean combustion gas containing substantially no UHOlCo and NOX was obtained. In this case, the temperature at a point 100M behind the catalyst layer reached about 1300°C, but the temperature at the outlet of the ISN layer was about 905°C.
引きつづき、３容量％相当分のメタンを触ａ層上流から
、残り １．１容量％相当分のメタン触媒層口より３０
ＩＩｌｌ＋後方から導入して、同様の燃焼実験を行った
（実験番号１）。Subsequently, methane equivalent to 3% by volume was added from upstream of the catalyst layer, and the remaining methane equivalent to 1.1% by volume was added to the catalyst layer from the inlet of the catalyst layer.
A similar combustion experiment was conducted by introducing IIll+ from the rear (experiment number 1).
その結果、触媒層出口温度は約８６０℃であり、クリー
ンな約１３００℃の燃焼ガスがえられた。またこの性能
は１０００時間にわたり維持継続した。As a result, the catalyst bed outlet temperature was about 860°C, and clean combustion gas of about 1300°C was obtained. Moreover, this performance was maintained continuously for 1000 hours.
実施例１０
実施例９と同様にして第１表のとおりの触媒を用い、３
容量％相当分のメタンを触媒層上流から、残り １．１
容量％相当分のメタンを触媒層出口より３０ｍｍ後方か
ら導入して燃焼実験を行った。結果は第１表のとおりで
あり、本発明による触媒体を用いれば触！Ｉ！層温度は
活性低下をおこさない１０００℃以下に維持されている
にもかかわらず約１３００℃のクリーンな燃焼ガスがえ
られたのに対し、ガス入口側に比較例１次いで比較例２
、ガス出口側に比較例５で得られた触媒を用いた場合（
実験番号８）触媒層出口温度は４９０℃で２次燃焼が誘
発される温度には上昇できず、触媒層後方１００４！Ｉ
ＩＩの点の温度は４８０℃で燃焼効率も約１５％であっ
た
中段触媒層に実施例３で得られた触媒を用いた実験番号
１１の結果、パラジウムおよび白金の全担持量が担体容
積１ｊ！あたり１０９を下回るので、燃焼活性は劣って
おり、燃焼効率は４１％であった。Example 10 In the same manner as in Example 9, using the catalyst shown in Table 1, 3
Methane equivalent to volume % is removed from upstream of the catalyst layer, and the remaining 1.1
A combustion experiment was conducted by introducing methane equivalent to % by volume from 30 mm behind the outlet of the catalyst layer. The results are shown in Table 1, and it is clear that using the catalyst according to the present invention! I! Clean combustion gas of approximately 1300°C was obtained despite the fact that the bed temperature was maintained below 1000°C, which does not cause a decrease in activity.
, when the catalyst obtained in Comparative Example 5 was used on the gas outlet side (
Experiment No. 8) The catalyst layer outlet temperature was 490°C and could not rise to a temperature that would induce secondary combustion, and the temperature at the rear of the catalyst layer was 1004! I
The temperature at point II was 480°C and the combustion efficiency was about 15%.As a result of experiment number 11 using the catalyst obtained in Example 3 in the middle catalyst layer, the total amount of palladium and platinum supported was 1j of the carrier volume. ! The combustion activity was poor, and the combustion efficiency was 41%.
又、前段触媒に実施例５で得られた触媒を用いた実験番
号１２の結果もニッケル酸化物が担持されていない触媒
体であるため、触媒層出口温度は７２０℃であり一部２
次燃焼は誘発されているが１００Ｎ１１後方の点温度は
９８０℃で燃焼効率も６６％であった。In addition, the results of experiment number 12 using the catalyst obtained in Example 5 as the front stage catalyst also showed that the catalyst layer did not support nickel oxide, so the catalyst layer outlet temperature was 720°C, and some 2
Although the secondary combustion was induced, the point temperature behind the 100N11 was 980°C and the combustion efficiency was 66%.
さらに後段触媒に比較例６で得られた触媒を用いた実験
番号１３の結果はパラジウムおよび白金の全担持量が担
体容積１１あたり１００ｇを上回り、後段触媒層温度が
１０３０℃と１０００℃を越えたため約５０時間経過後
から活性が低下し、３００時間で後段触媒は失活した。Furthermore, the results of Experiment No. 13 using the catalyst obtained in Comparative Example 6 as the rear stage catalyst showed that the total supported amount of palladium and platinum exceeded 100 g per carrier volume 11, and the rear stage catalyst layer temperature exceeded 1030°C and 1000°C. The activity decreased after about 50 hours, and the latter catalyst was deactivated after 300 hours.
Claims (22)
高線速の可燃性混合ガスの流れに対して、ガス入口側に
パラジウム、白金およびニッケル酸化物を活性成分とす
る前段触媒層、ガス出口側に白金を活性成分とする、あ
るいは白金およびパラジウムを活性成分とする後段触媒
層を組合せた触媒システムからなり、該触媒システムに
担持されたパラジウムおよび白金の合計の全担持量が担
体容積１ｌあたり１０〜１００ｇであることを特徴とす
る高圧メタン系燃料の燃焼用触媒システム。(1) For the flow of a high-pressure, high-linear velocity combustible mixed gas consisting of methane-based fuel and molecular oxygen-containing gas, a pre-catalyst layer containing palladium, platinum and nickel oxide as active components is placed on the gas inlet side, and the gas It consists of a catalyst system in which a post-catalyst layer containing platinum as an active ingredient or platinum and palladium as active ingredients is combined on the outlet side, and the total amount of palladium and platinum supported on the catalyst system is 1 liter in carrier volume. A catalyst system for combustion of high-pressure methane-based fuel, characterized in that the amount is 10 to 100 g per liter.
積１ｌあたり１０〜１５０ｇであることを特徴とする特
許請求の範囲（１）記載の触媒システム。(2) The catalyst system according to claim (1), wherein the amount of nickel oxide supported in the first stage catalyst layer is 10 to 150 g per liter of carrier volume.
量に対して１〜２５なる担持比であることを特徴とする
特許請求の範囲（１）記載の触媒システム(3) The catalyst system according to claim (1), characterized in that the amount of palladium supported in the first stage catalyst layer is a support ratio of 1 to 25 with respect to the amount of platinum supported.
性成分とする場合、パラジウムの担持量は白金の担持間
に対して０．１〜１０なる担持比であることを特徴とす
る特許請求の範囲（１）記載の触媒システム。(4) When platinum and palladium are used as active components in the latter catalyst layer, the amount of palladium supported is at a ratio of 0.1 to 10 to the amount of supported platinum ( 1) Catalyst system as described.
ス担体に分散担持されてなる特許請求の範囲（１）記載
の触媒システム。(5) The catalyst system according to claim (1), wherein each active component is dispersed and supported on a monolithic carrier coated with alumina.
ウム、ネオジム、プラセオジム、カルシウム、ストロン
チウム、バリウムおよびシリカよりなる群から選ばれた
少なくとも１種の酸化物によって安定化されてなる特許
請求の範囲（１）記載の触媒システム。(6) Claim (1) wherein the alumina coating layer is stabilized with at least one oxide selected from the group consisting of lanthanum, cerium, samarium, neodymium, praseodymium, calcium, strontium, barium, and silica. ) described catalyst system.
システムである特許請求の範囲（１）記載の触媒システ
ム。(7) The catalyst system according to claim (1), wherein the catalyst system is a catalyst system for fuel combustion of a gas turbine.
高線速の可燃性混合ガスの流れに対して、ガス入口側に
パラジウム、白金およびニッケル酸化物を活性成分とす
る前段触媒層、およびガス出口側に白金を活性成分とす
る、あるいは白金およびパラジウムを活性成分とする後
段触媒層を組合せた触媒システムからなり、該触媒シス
テムに担持された白金およびパラジウムの合計の全担持
量が担体容積１ｌあたり１０〜１００ｇである高圧メタ
ン系燃料の燃焼用触媒システムを用い、該触媒システム
において、メタン系燃料の一部のみを燃焼せしめて２次
燃焼が誘発される温度にまで燃焼ガスを昇温させること
を特徴とする燃焼方法。(8) For the flow of a high-pressure, high-linear velocity combustible mixed gas consisting of methane-based fuel and molecular oxygen-containing gas, a pre-stage catalyst layer containing palladium, platinum and nickel oxide as active components is provided on the gas inlet side; The catalyst system consists of a combination of a post-catalyst layer containing platinum as an active ingredient or platinum and palladium as active ingredients on the gas outlet side, and the total amount of platinum and palladium supported on the catalyst system is the carrier volume. Using a catalyst system for combustion of high-pressure methane-based fuel at a rate of 10 to 100 g per liter, the combustion gas is heated in the catalyst system to a temperature at which only a portion of the methane-based fuel is combusted and secondary combustion is induced. A combustion method characterized by:
燃焼ガス温度を前段触媒層において６００〜９００℃、
後段触媒層において７５０〜１０００℃まで上昇させる
ことを特徴とする燃焼方法。(9) In the combustion method described in claim (8),
The combustion gas temperature is set at 600 to 900°C in the front catalyst layer.
A combustion method characterized by raising the temperature to 750 to 1000°C in the latter stage catalyst layer.
さらに２次燃料を供給して、２次燃焼せしめることを特
徴とする特許請求の範囲（８）記載の方法。(10) The method according to claim (8), characterized in that secondary fuel is further supplied to the gas heated to a temperature that induces secondary combustion to cause secondary combustion.
、該可燃性混合ガスが５〜３０ａｔａの圧力を有し、触
媒体入口への線速が５００℃換算で５〜４０ｍ／秒なる
条件であることを特徴とする燃焼方法。(11) In the combustion method according to claim (8), the combustible mixed gas has a pressure of 5 to 30 ata, and the linear velocity to the inlet of the catalyst is 5 to 40 m/sec in terms of 500°C. A combustion method characterized by:
圧高線速の可燃性混合ガスの流れに対して、ガス入口側
にパラジウム、白金およびニッケル酸化物を活性成分と
する前段触媒層、次いでパラジウムおよび白金を活性成
分とする、あるいはパラジウムおよびニッケル酸化物を
活性成分とする中段触媒層、最後にガス出口側に白金を
活性成分とする、あるいは白金およびパラジウムを活性
成分とする後段触媒層を組合せた触媒システムからなり
、該触媒システムに担持されたパラジウムおよび白金の
合計の全担持量が担体容積１ｌあたり１０〜１００ｇで
あることを特徴とする高圧メタン系燃料の燃焼用触媒シ
ステム。(12) For the flow of a high-pressure, high-linear velocity combustible mixed gas consisting of methane fuel and molecular oxygen-containing gas, a pre-catalyst layer containing palladium, platinum and nickel oxide as active components is placed on the gas inlet side, and then A middle catalyst layer containing palladium and platinum as active ingredients or palladium and nickel oxide as active ingredients, and finally a rear catalyst layer containing platinum as active ingredients or platinum and palladium on the gas outlet side. 1. A catalyst system for combustion of high-pressure methane-based fuels, comprising a combined catalyst system, characterized in that the total amount of palladium and platinum supported on the catalyst system is 10 to 100 g per liter of support volume.
化物の担持量が担体容積１ｌあたり１０〜１５０ｇであ
ることを特徴とする特許請求の範囲（１２）記載の触媒
システム。(13) The catalyst system according to claim (12), wherein the amount of nickel oxide supported in the first catalyst layer and the middle catalyst layer is 10 to 150 g per liter of carrier volume.
の担持量は白金の担持量に対して１〜２５なる担持比で
あることを特徴とする特許請求の範囲（１２）記載の触
媒システム。(14) The catalyst system according to claim (12), wherein the amount of palladium supported in the first catalyst layer and the middle catalyst layer is at a ratio of 1 to 25 relative to the amount of platinum supported.
活性成分とする場合、パラジウムの担持量は白金の担持
量に対して０．１〜１０なる担持比であることを特徴と
する特許請求の範囲（１２）記載の触媒システム。(15) When platinum and palladium are used as active components in the latter catalyst layer, the amount of palladium supported is at a ratio of 0.1 to 10 with respect to the amount of platinum supported ( 12) Catalyst system as described.
リス担体に分散担持されてなる特許請求の範囲（１２）
記載の触媒システム。(16) Claim (12) in which each active ingredient is dispersed and supported on a monolithic carrier coated with alumina.
Catalyst system as described.
リウム、ネオジム、プラセオジム、カルシウム、ストロ
ンチウム、バリウムおよびシリカよりなる群から選ばれ
た少なくとも１種の酸化物によって安定化されてなる特
許請求の範囲（１２）記載の触媒システム。(17) Claim (12) wherein the alumina coating layer is stabilized with at least one oxide selected from the group consisting of lanthanum, cerium, samarium, neodymium, praseodymium, calcium, strontium, barium, and silica. ) described catalyst system.
媒システムである特許請求の範囲（１２）記載の触媒シ
ステム。(18) The catalyst system according to claim (12), wherein the catalyst system is a catalyst system for fuel combustion of a gas turbine.
圧高線速の可燃性混合ガスの流れに対してガス入口側に
パラジウム、白金およびニッケル酸化物を活性成分とす
る前段触媒層、次いでパラジウムおよび白金を活性成分
とする、あるいはパラジウムおよびニッケル酸化物を活
性成分とする中段触媒層、最後にガス出口側に白金を活
性成分とする、あるいは白金およびパラジウムを活性成
分とする後段触媒層を組合せた触媒システムからなり、
該触媒システムに担持された白金およびパラジウムの合
計の全担持量が担体容積１ｌあたり１０〜１００ｇであ
る高圧メタン系燃料の燃焼用触媒システムを用い、該触
媒システムにおいて、メタン系燃料の一部のみを燃焼せ
しめて２次燃焼が誘発される温度にまで燃焼ガスを昇温
させることを特徴とする燃焼方法。(19) For the flow of a high-pressure, high-linear velocity combustible mixed gas consisting of methane-based fuel and molecular oxygen-containing gas, a first-stage catalyst layer containing palladium, platinum, and nickel oxide as active components is placed on the gas inlet side, and then palladium and a middle catalyst layer containing platinum as an active ingredient or palladium and nickel oxide as active ingredients, and finally a rear catalyst layer on the gas outlet side containing platinum as an active ingredient or platinum and palladium as active ingredients. The catalyst system consists of
A catalyst system for combustion of high-pressure methane-based fuel is used, in which the total amount of platinum and palladium supported on the catalyst system is 10 to 100 g per liter of carrier volume, and in the catalyst system, only a portion of the methane-based fuel is used. A combustion method characterized by raising the temperature of combustion gas to a temperature that induces secondary combustion.
て、燃焼ガス温度を前段触媒層において６００〜８００
℃、中段触媒層において６５０〜９００℃、後段触媒層
において８００〜１０００℃まで昇温させることを特徴
とする燃焼方法。(20) In the combustion method according to claim (19), the combustion gas temperature is set to 600 to 800 in the front catalyst layer.
A combustion method characterized by raising the temperature to 650-900°C in the middle catalyst layer and 800-1000°C in the latter catalyst layer.
さらに２次燃料を供給して、２次燃焼せしめることを特
徴とする特許請求の範囲（１９）記載の燃焼方法。(21) The combustion method according to claim (19), characterized in that secondary combustion is caused by further supplying secondary fuel to the gas heated to a temperature that induces secondary combustion.
て、該可燃性混合ガスが５〜３０ａｔａの圧力を有し、
触媒システム入口への線速が５００℃換算で５〜４０ｍ
／秒なる条件であることを特徴とする燃焼方法。(22) In the combustion method according to claim (19), the combustible mixed gas has a pressure of 5 to 30 ata,
The linear velocity to the catalyst system inlet is 5 to 40 m at 500°C.
A combustion method characterized by a condition of / seconds.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61224837A JPS6380849A (en) | 1986-09-25 | 1986-09-25 | Catalytic system for combustion of high pressure methane based fuel and combustion method using the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61224837A JPS6380849A (en) | 1986-09-25 | 1986-09-25 | Catalytic system for combustion of high pressure methane based fuel and combustion method using the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6380849A true JPS6380849A (en) | 1988-04-11 |
| JPH0545295B2 JPH0545295B2 (en) | 1993-07-08 |
Family
ID=16819953
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61224837A Granted JPS6380849A (en) | 1986-09-25 | 1986-09-25 | Catalytic system for combustion of high pressure methane based fuel and combustion method using the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6380849A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248251A (en) * | 1990-11-26 | 1993-09-28 | Catalytica, Inc. | Graded palladium-containing partial combustion catalyst and a process for using it |
| US5250489A (en) * | 1990-11-26 | 1993-10-05 | Catalytica, Inc. | Catalyst structure having integral heat exchange |
| US5258349A (en) * | 1990-11-26 | 1993-11-02 | Catalytica, Inc. | Graded palladium-containing partial combustion catalyst |
| US5259754A (en) * | 1990-11-26 | 1993-11-09 | Catalytica, Inc. | Partial combustion catalyst of palladium on a zirconia support and a process for using it |
| US5281128A (en) * | 1990-11-26 | 1994-01-25 | Catalytica, Inc. | Multistage process for combusting fuel mixtures |
| US5368835A (en) * | 1992-08-14 | 1994-11-29 | Council Of Scientific & Industrial Research | Process for production of synthesis gas by oxidative conversion of methane or natural gas using composite catalysts |
| US5511972A (en) * | 1990-11-26 | 1996-04-30 | Catalytica, Inc. | Catalyst structure for use in a partial combustion process |
| CN105797766A (en) * | 2016-04-21 | 2016-07-27 | 中广核研究院有限公司 | Integrated catalyst applied to catalytic combustion of methane and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6456328A (en) * | 1987-08-26 | 1989-03-03 | Seiko Epson Corp | Production of quartz crucible |
-
1986
- 1986-09-25 JP JP61224837A patent/JPS6380849A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6456328A (en) * | 1987-08-26 | 1989-03-03 | Seiko Epson Corp | Production of quartz crucible |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5248251A (en) * | 1990-11-26 | 1993-09-28 | Catalytica, Inc. | Graded palladium-containing partial combustion catalyst and a process for using it |
| US5250489A (en) * | 1990-11-26 | 1993-10-05 | Catalytica, Inc. | Catalyst structure having integral heat exchange |
| US5258349A (en) * | 1990-11-26 | 1993-11-02 | Catalytica, Inc. | Graded palladium-containing partial combustion catalyst |
| US5259754A (en) * | 1990-11-26 | 1993-11-09 | Catalytica, Inc. | Partial combustion catalyst of palladium on a zirconia support and a process for using it |
| US5281128A (en) * | 1990-11-26 | 1994-01-25 | Catalytica, Inc. | Multistage process for combusting fuel mixtures |
| US5405260A (en) * | 1990-11-26 | 1995-04-11 | Catalytica, Inc. | Partial combustion catalyst of palladium on a zirconia support and a process for using it |
| US5511972A (en) * | 1990-11-26 | 1996-04-30 | Catalytica, Inc. | Catalyst structure for use in a partial combustion process |
| US5368835A (en) * | 1992-08-14 | 1994-11-29 | Council Of Scientific & Industrial Research | Process for production of synthesis gas by oxidative conversion of methane or natural gas using composite catalysts |
| US5411927A (en) * | 1992-08-14 | 1995-05-02 | Council Of Scientific & Industrial Research | Process of preparing composite catalysts for production of synthesis gas by oxidative conversion of methane or natural gas |
| CN105797766A (en) * | 2016-04-21 | 2016-07-27 | 中广核研究院有限公司 | Integrated catalyst applied to catalytic combustion of methane and preparation method thereof |
| CN105797766B (en) * | 2016-04-21 | 2019-08-30 | 中广核研究院有限公司 | Integral catalyzer and preparation method thereof for methane catalytic combustion |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0545295B2 (en) | 1993-07-08 |
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